CN101003019A - Method for preparing anode catalyst of direct methanol fuel cell - Google Patents
Method for preparing anode catalyst of direct methanol fuel cell Download PDFInfo
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Abstract
A process for preparing the anode catalyst Pt/PANI/MWNT able to be directly used for methanol fuel battery includes such steps as adding sulfuric acid solution containing disperser into container, adding multi-wall carbon nanotubes, ultrasonic oscillating, adding phenylamine and ammonium persulfate solution, reacting, washing, baking to obtain polyphenylamine/multi-wall carbon nanotubes carrier, adding additive contained buffering solution of acetic acid, ultrasonic oscillating, adding chloroplatinic acid solution, continuous oscillating while heating and dropping sodium borohydride solution, reacting, filtering, washing and baking.
Description
Technical field
The present invention relates to a kind of fuel battery anode catalyst, particularly relating to a kind of is carrier with polyaniline/multi-walled carbon nano-tubes (PANI/MWNT) composite, and at the loaded catalyst (Pt/PANI/MWNT) of its surface deposition platinum (Pt), and with the preparation method of this loaded catalyst as DMFC (DMFC) anode catalyst.
Background technology
The puzzlement of " energy crisis " and people are to the pay attention to day by day of environmental protection, and seeking a kind of new " clean energy resource " has become global new problem.Fuel cell is generally believed it is the novel energy of a kind of " green ", has great importance to improving resource utilization and solving environmental pollution.
DMFC (Direct Methanol Fuel Cell, DMFC) be a kind of TRT that the chemical energy of fuel (methyl alcohol) and oxidant (air or oxygen) is directly changed into electric energy, have energy density and power density height and the low advantage of operating temperature, but also have the cost height, easily poison and the easy shortcoming such as infiltration of methyl alcohol.At present, the subject matter of DMFC existence is: 1) the catalytic oxidation speed of fuel methanol is slower under the normal temperature, and noble metal electrocatalyst is easily poisoned by carbon monoxide (CO) class intermediate product, and current density is lower.2) noble metal costs an arm and a leg, and catalyst volume production cost is too high.The permeability of first alcohol and water from anode to negative electrode is higher when 3) battery operated.4) hydro-thermal complex management, service life is still undesirable.As seen, the research and development of eelctro-catalyst is a key problem in technology of realizing " application ".Platinum is the most suitable catalyst in the DMFC system, and with regard to present situation, it is its two large problems that faces that catalyst poisoning, the performance that utilization ratio that platinum catalyst is low and the absorption of CO toxicity intermediate cause descends.
Have in the main approaches of improving catalyst activity and anti-poisoning capability both at home and abroad: 1) platinum alloy technology; 2) development of new carbon support material; 3) with the conducting polymer be carrier.Adopt the platinum base alloy catalyst to poison and improve and obtain certain effect aspect active, yet its unstability and preparation technology's enforcement and high preparation cost make it also quite far away from industrialized distance anti-.Adopt carbon carrier (comprising carbon black, carbon fiber, CNT etc.) loaded catalyst can reduce the platinum carrying capacity greatly, improve its utilization rate, agglomeration influences catalytic efficiency (Roy S C but this class carrier is because of defective own makes catalyst granules occur largely, Christensen P A, Hamnett A, Thomas K M, Trapp V. J.Electrochem Soc.[J], 1996,143 (10): 3073-3079).
In recent years, increasing research concentrates in the seeking and attempt of novel catalyst carrier, and is convenient to suitability for industrialized production with hope when improving catalytic activity.The develop rapidly of conducting polymer research has attracted numerous researchers' sight.Polyaniline (PANI) is one of conducting polymer with fastest developing speed in this field, and it is synthetic simple and easy, has good electro-chemical activity and environmental stability.Adopt PANI to become instantly one of popular topic as the carrier of platinum Base Metal particle among the DMFC.
People such as Zhou Haihui (Zhou Haihui, Jiao Shuqiang, Chen Jinhua. Acta PhySico-Chimica Sinica .2004,20 (1): 9-14) the nanometer fibrous PANI with the pulse current method preparation is the platinum particles carrier, prepared the anodised catalysis electrode of methyl alcohol with it, result of study shows that the electrode pair methanol oxidation has good electro catalytic activity, and the concerted catalysis effect is arranged.
T.Kessler and A.M.Castro Luna (T.Kessler.A.M.Castro Luna.J Solid StateElectrochem.2003,7:593-598) has certain thickness PANI membrane electrode with the cyclic voltammetry preparation, and be carrier electrochemical deposition platinum and alloy catalyst thereof, particle diameter is about 100nm.Compared the catalytic performance of various catalyst to methanol oxidation.Catalyst shown in the literary composition to the current density of anodic oxidation of methanol basically at 1mA/cm
2Below, can think that this is because the simple low electrical conductivity of PANI causes.
People such as B.Rajesh (B.Rajesh, K.Ravindranathan Thampi, J.M.Bonard, etal.Electrochemical and Solid-State Letters.2004,7 (11): A404-A407) electricity consumption chemical template method synthesis of nano tubulose PANI is on industrial carbon cloth, the back is a carrier electrochemical deposition platinum with it, and particle diameter is 100～150nm.Studied the electrocatalytic oxidation property of catalyst with chronoamperometry, compared, shown that its attenuation degree alleviates with traditional Pt/C catalyst to methyl alcohol.
People (Liu Niu such as Lin Niu, Qiuhong Li, Fenghua Wei, et al.Journal of ElectroanalyticalChemistry.2005 578:331-337) deposits platinum catalyst by a series of electrochemical method (as cyclic voltammetry, two step timing electric weight and potentiostatic method) on the synthetic PANI membrane electrode of cyclic voltammetry electrochemistry.Studied catalytic oxidation, shown to have certain synergy between platinum particles and the PANI, thereby promoted the raising of catalytic performance methyl alcohol.
Comprehensive literature report, correlative study all is based on the film modified electrode of electrochemical production PANI, again with the platinum particles electro-deposition to the PANI film.The method no doubt to platinum particles on the PANI film dispersion and the control of particle diameter is greatly improved, yet the restriction of electrode area makes its very difficult suitability for industrialized production.In addition, single use conducting polymer is as the carrier of platinum class catalyst, and the limitation of its electronic conduction ability weakens the current density of whole catalystic converter system greatly.
Along with constantly development of composite research, employing CNT and polyaniline are compound by different way to become a kind of novel catalyst carrier that is expected to substitute simple CNT and simple polyaniline, and the work of this respect does not have relevant report both at home and abroad so far.At metal particle on common carbon carrier, easily reunite, the effective little and metallic catalyst of catalysis area problem such as poisoning easily, electronic conductive polymer and CNT are compounded to form the cladding nanometer tubular construction, the active carrier of a high-ratio surface is provided for the metal particle deposition, polyaniline (PANI) class conducting polymer self has redox active, can change the state of platinum metallics such as (Pt) deposition, improve its anti-carbon monoxide (CO) poisoning capability.Difficult point is to prevent that the reunion because of polymer in the building-up process from reduce specific area greatly and influencing load effect.
Preparation method about polyaniline and carbon nano tube compound material reports a lot, as: people such as Feng Wei (seal big, Yi Wenhui, Xu Youlong. Acta Physica Sinica .2003,52 (5): 1272-1276) adopt the emulsion dispersion in-situ polymerization to prepare polyaniline/multi-wall carbon nano-tube tube complex (PANI/MWNT), wherein the MWNT/PANI mass ratio is 1/5, and photoresponse, electrical property, photoelectric respone and the molecular conformation of this compound studied in great detail.People such as Liu Jiaan (Liu Jiaan, Zhou Liang, Liu Jiping. New Chemical Materials .2004,32 (5): 13-15) adopt situ aggregation method to synthesize polyaniline and polyaniline/carbon nano tube compound material, investigated the influence of different CNT additions (1%, 5%, 10%) p-poly-phenyl amine/carbon nano tube compound material configuration of surface, material structure and electric conductivity and characterize with high electrical conductivity.S.J.Park etc. (S.J.Park, S.Y.Park, M.S.Cho, et al.Synthetic Metals.2005 152:337-340) adopts dispersion oxidation polymerization to prepare polyaniline/multi-walled carbon nano-tubes (PANI/MWNT) composite nanoparticle.Adopt polyvinyl alcohol (PVA) as polymerization stabilizer in the process, hydrochloric acid (HCl) solution is as reaction medium and mix acid, and the addition of MWNT is 0.1% (mass percent) of aniline (ANI).
The comprehensive literature report, chemical situ aggregation method is implemented simple and easy, and is compound even, meets the suitability for industrialized production requirement.But, the report that the chemical in-situ polymerization of nearly all utilization prepares the PANI/MWNT composite is all considered at aspect of performances such as the conduction of composite, mechanics, photoelectricity, and mostly be based on polymer, CNT is dispersed in polymer network the inside as " filler " and plays the effect that strengthens and improve electric conductivity, and the composite that none considers preparation in this way is used for DMFC (DMFC) as the carrier of platinum class catalyst.On the other hand, about Preparation of catalysts, the method that is fit to the industrialization direction is a chemical deposition.Relate to the consideration of series of factors in the process, as reducing agent type and ratio, reaction medium, reaction temperature, reaction time and product postprocessing or the like.In must the consideration process when adopting the PANI/MWNT composite as the platinum particles carrier aqueous solution of carrier again scattering problem and preparation condition to the Adsorption Effect of catalyst precursor on carrier.
Therefore, the scheme of appropriate design polyaniline/multi-walled carbon nano-tubes (PANI/MWNT) composite carrier load platinum particulate just becomes this class composite obtains extensive use in the DMFC catalyst field key technology.
Summary of the invention
The objective of the invention is at existing many deficiencies in the existing DMFC method for preparing catalyst, providing a kind of is the preparation method of the Pt/PANI/MWNT support type DMFC anode catalyst of carrier with polyaniline/multi-walled carbon nano-tubes (PANI/MWNT) composite.
DMFC anode catalyst of the present invention is made up of complex carrier and metallic two parts, wherein, complex carrier is through chemical in-situ polymerization and polyaniline/multi-walled carbon nano-tubes (PANI/MWNT) composite of cooperating dispersant (Triton X-100 or polyvinyl alcohol) to be prepared from, and aniline monomer (ANI) is (0.67～2) with MWNT rate of charge (mass ratio): 1; Metal in the catalyst is platinum (Pt); Need catalyst precursor, reducing agent, reducing medium and additive in catalyst preparation process, it is 10%～40% that the gained catalyst carries the platinum amount.
The present invention includes following steps:
1) preparation complex carrier: in reaction vessel, add the sulfuric acid solution that contains dispersant earlier, add multi-walled carbon nano-tubes again, add aniline behind the sonic oscillation, add ammonium persulfate solution again, 0～5 ℃ of reaction back washing down, oven dry, standby.Described dispersant is selected at least a in Triton X-100 and the polyvinyl alcohol for use, by quality than dispersant: aniline: multi-walled carbon nano-tubes=(1～2): (0.67～2): 1.
2) get polyaniline/multi-walled carbon nano-tubes complex carrier powder to reaction vessel, add the acetate buffer solution that contains additive, sonic oscillation gets dispersion liquid.Described additive is at least a in ethylene glycol, the isopropyl alcohol, the pH=3.5 of acetate buffer solution～4.5.
3) get chloroplatinic acid (H
2PtCl
6) solution adds in the dispersion liquid, continues vibration, by quality than chloroplatinic acid: polyaniline/multi-walled carbon nano-tubes complex carrier powder=(0.23～1.4): 1.
4) be warming up to 60～80 ℃, splash into excessive sodium borohydride reduction agent solution reaction back and filter, washing is not dried finished product after having chlorion.
In step 1), the sonic oscillation time is 2～4h, and 2.4 times of the suitable aniline quality of the addition of ammonium persulfate solution are 6～8h 0～5 ℃ of following reaction time.The concentration of multi-walled carbon nano-tubes in sulfuric acid solution is 0.5～1mg/ml, and sulfuric acid solution concentration is 1mol/L.
In step 2) in, the sonic oscillation time that adds behind the acetate buffer solution contain additive is 2～4h.Polyaniline/the concentration of multi-walled carbon nano-tubes complex carrier powder in acetate buffer solution is 0.5～1mg/ml, and additive capacity is 10%～20% of an acetate buffer solution.
In step 3), the continuation duration of oscillation is 30～60min, and the concentration of chloroplatinic acid is 0.0386～0.077mmol/L.
In step 4), the time that splashes into excessive sodium borohydride reduction agent solution reaction is 1～2h, and bake out temperature is 70～80 ℃.
In the DMFC anode catalyst of the present invention the Pt particle present efficiently in the dispersion of carrier surface, the nanoscale particle of homogeneous, have methanol oxidation catalytic activity preferably, and toxicity improves greatly among the anti-CO of more traditional carbon supported platinum catalyst.In polyaniline/multi-walled carbon nano-tubes (PANI/MWNT) complex carrier, MWNT is controlling the morphosis of carrier material, and PANI attached to the MWNT surface, has largely improved the surface nature of carrier as a kind of dressing agent.On physical angle, the macromolecular chain of PANI is wrapped in around the MWNT, makes MWNT present coarse microcosmic surface, makes to possess very that the specific area of the MWNT of bigger serface is further improved, thereby has improved the deposition efficiency of platinum greatly.On chemical terms, PANI has the absorption that is beneficial to water in the solution and generates active oxygenated species Pt-OH
Ad, impel the CO of absorption to be oxidized to CO
2And desorption comes out, thereby has reached the effect that anti-CO poisons.Simultaneously, the existence of PANI improves the dispersiveness of Pt particulate on carrier greatly, and this platinum particles that is in high dispersion state is difficult for poisoning because of the minimizing of middle toxic substance adsorption site; The film modified electrode of PANI has quickened the Langmuir of methyl alcohol on electrode and has adsorbed the effect of also having played co-catalyst.In addition, exist certain cooperative effect to impel the raising of catalytic performance between PANI and the platinum particles.
The present invention is used for the catalytic oxidation process of methyl alcohol with the carrier of polyaniline/carbon nano tube compound material as noble metal platinum, has following outstanding advantage:
1. utilize chemical situ aggregation method to prepare the PANI/MWNT complex carrier, use the surface deposition platinum of chemical reduction method then, this preparation technology technical scale production that suits at the PANI/MWNT complex carrier.
2. to have selected be the PANI/MWNT complex carrier of matrix material with MWNT, avoided because the winding and the CNT of polymer network are easily reunited, hinder complex carrier in the aqueous solution dispersion so that influence the generation that supported catalyst prepares phenomenon.Referring to Fig. 1 as seen, under identical multiplication factor, the diameter of PANI/MWNT increases than MWNT diameter; (referring to Fig. 2) shown the basic chemical structure of PANI: 1590cm in the compound in the sample F T-IR spectrum behind the purifying
-1, 1499cm
-1The absworption peak of the corresponding quinoid structure of difference (N=Q=N) and the characteristic absorption peak of benzene formula structure (N-B-N); 1310cm
-1With 1245 be due to the absorption of aromatic amine Ar-N; 830cm
-1And 1135cm
-1The peak is respectively the outer and in-plane bending vibration characteristic absorption band of the face of contraposition phenyl ring.
The dispersion of Pt particle on its surface presents efficiently, the nanoscale particle of homogeneous 3.PANI/MWNT complex carrier with its excellent surface characteristic, makes.Referring to Fig. 3 and 4, the Pt particle is evenly distributed on carrier surface with the cluster form that particle diameter is about 7nm.The 2 θ angles of (Fig. 5) are 39.9 °, 46.5 °, 67.8 °, 81.2 ° and locate in the XRD figure spectrum, and corresponding is [111], [200], [220], [311] crystal face diffraction maximum of Pt respectively.With the strongest Pt[111] half-peak breadth of crystal face diffraction maximum, the average grain diameter that can calculate platinum particles in the catalyst by the Scherrer formula is 7.31nm, the basically identical as a result that draws with SEM.)。
4. be the catalyst of preparing carriers with the PANI/MWNT composite, in catalytic oxidation process, demonstrate stronger anti-poisoning performance of more traditional platinum/carbon (Pt/C) catalyst and the catalytic activity of Geng Gao certain density methanol solution.Referring to Fig. 6, because of being subjected to the murder by poisoning of intermediate product CO, simple carbon carries platinum behind scan round 200 circles, and its current strength has descended 61.5%, and complex carrier carries platinum and only descends 12.3%, and its anti-poisoning capability is the former 5 times.This is having the absorption that is beneficial to water in the solution and generating active oxygenated species Pt-OH owing to polyaniline
Ad, impel the CO of absorption to be oxidized to CO
2And desorption comes out, thereby has reached the effect that anti-CO poisons.In addition, the existence of PANI improves the dispersiveness of Pt particulate on carrier greatly, and this catalyst particle that is in high dispersion state is difficult for poisoning because of the minimizing of middle toxic substance adsorption site.The polyaniline film modified electrode has quickened the Langmuir of methyl alcohol on electrode and has adsorbed the effect of also having played co-catalyst.
Description of drawings
Fig. 1 is the SEM figure of polyaniline/multi-walled carbon nano-tubes complex carrier and multi-walled carbon nano-tubes carrier.In Fig. 1, a is the SEM figure of polyaniline/multi-walled carbon nano-tubes complex carrier, and b is the SEM figure of multi-walled carbon nano-tubes carrier.
Fig. 2 is the FTIR figure of polyaniline/multi-walled carbon nano-tubes complex carrier and multi-walled carbon nano-tubes carrier.In Fig. 2, curve a is the FTIR figure of polyaniline/multi-walled carbon nano-tubes complex carrier, and curve b is the FTIR figure of multi-walled carbon nano-tubes carrier, and abscissa is wave number cm
-1
Fig. 3 is the SEM figure of DMFC anode catalyst.
Fig. 4 is the partial enlarged drawing of Fig. 3.
Fig. 5 is the XRD figure of polyaniline/multi-walled carbon nano-tubes complex carrier (PANI/MWNT) and DMFC anode catalyst (Pt/PANI/MWNT).
Fig. 6 is at 1.0mol/L H
2SO
4+ 1.0mol/LCH
3CV decay pattern in the OH solution.In Fig. 6, a is platinum/XC-72 carbon black catalyst (Pt/C), 200 circles; B is catalyst of the present invention (Pt/PANI/MWNT), 200 circles.Abscissa is Potential/V (vs.SCE), and ordinate is Current/A.
The specific embodiment
Embodiment 1:
(1) preparation of complex carrier: with single neck flask is reaction vessel, add the 1mol/L sulfuric acid solution that 100ml contains the 0.1g polyvinyl alcohol earlier, add 0.1gMWNT, sonic oscillation 4h under the room temperature, the back adds 0.067gANI, slowly drips ammonium persulfate (APS) solution of 2.4 times of aniline amounts again.React 8h down at 0 ℃.Washing, oven dry, standby.The SEM figure of polyaniline/multi-walled carbon nano-tubes complex carrier and multi-walled carbon nano-tubes carrier is referring among Fig. 1, and wherein a is the SEM figure of polyaniline/multi-walled carbon nano-tubes complex carrier, and b is the SEM figure of multi-walled carbon nano-tubes carrier.The FTIR figure of polyaniline/multi-walled carbon nano-tubes complex carrier and multi-walled carbon nano-tubes carrier is referring to Fig. 2, and wherein curve a is the FTIR figure of polyaniline/multi-walled carbon nano-tubes complex carrier, and curve b is the FTIR figure of multi-walled carbon nano-tubes carrier.
(2) the PANI/MWNT complex carrier powder of getting 0.1g adds the acetate buffer solution (pH=4) that 100ml contains 20% isopropyl alcohol to reaction bulb, and sonic oscillation 2h is up to being uniform dispersion.
(3) measure the chloroplatinic acid (H of 0.825ml 0.077mol/L
2PtCl
6) solution in dispersion liquid, continue vibration 60min.
(4) be warming up to 80 ℃, splash into excessive sodium borohydride solution, filter behind the reaction 1hr, washing is not dried finished product in 70 ℃ of vacuum drying ovens after having chlorion.
The SEM figure of resulting DMFC anode catalyst is referring to Fig. 3, and its partial enlarged drawing is referring to Fig. 4, and as seen from Figure 4, the Pt particle that is deposited on the PANI/MWNT carrier surface is high-visible.The XRD figure of polyaniline/multi-walled carbon nano-tubes complex carrier (PANI/MWNT) and DMFC anode catalyst (Pt/PANI/MWNT) is referring to Fig. 5.At 1.0mol/L H
2SO
4+ 1.0mol/LCH
3CV decay pattern in the OH solution is referring to Fig. 6, and in Fig. 6, a is platinum/XC-72 carbon black catalyst (Pt/C), 200 circles; B is catalyst of the present invention (Pt/PANI/MWNT), 200 circles.
Embodiment 2～5: the consumption of chloroplatinic acid in the input amount of ANI and MWNT and polyvinyl alcohol consumption and the platinum deposition process in the change PANI/MWNT complex carrier preparation process, other condition is constant, sees Table 1.
Table 1
| Embodiment | ANI/g | MWNT/g | Polyvinyl alcohol/g | 0.077mol/L platinum acid chloride solution/ml |
| 2 | 0.1 | 0.1 | 0.1 | 1.65 |
| 3 | 0.1 | 0.1 | 0.15 | 2.475 |
| 4 | 0.15 | 0.1 | 0.1 | 1.65 |
| 5 | 0.2 | 0.1 | 0.2 | 3.3 |
Embodiment 6:
(1) preparation of complex carrier: with single neck flask is reaction vessel, add the 1mol/L sulfuric acid solution that 100ml contains the 0.1g Triton X-100 earlier, add 0.1gMWNT, sonic oscillation 4h under the room temperature, the back adds 0.067gANI, slowly drips ammonium persulfate (APS) solution of 2.4 times of aniline amounts again.React 8h down at 0 ℃.Washing, oven dry, standby.
(2) the PANI/MWNT complex carrier powder of getting 0.1g adds the acetate buffer solution (pH=3.5) that 100ml contains 10% isopropyl alcohol to reaction bulb, and sonic oscillation 2h is up to being uniform dispersion.
(3) measure the chloroplatinic acid (H of 3.3ml 0.0386mol/L
2PtCl
6) solution in dispersion liquid, continue vibration 60min.
(4) be warming up to 60 ℃, splash into excessive sodium borohydride solution, filter behind the reaction 1.5hr, washing is not dried finished product in 80 ℃ of vacuum drying ovens after having chlorion.
Embodiment 7～10: the consumption of chloroplatinic acid in the input amount of ANI and MWNT and Triton X-100 consumption and the platinum deposition process in the change PANI/MWNT complex carrier preparation process, other condition is constant, sees Table 2.
Table 2
| Embodiment | ANI/g | MWNT/g | Triton X-100/g | 0.0386mol/L platinum acid chloride solution/ml |
| 7 | 0.1 | 0.1 | 0.1 | 3.3 |
| 8 | 0.1 | 0.1 | 0.15 | 4.95 |
| 9 | 0.15 | 0.1 | 0.1 | 3.3 |
| 10 | 0.2 | 0.1 | 0.2 | 6.6 |
Claims (9)
1. DMFC method for preparing anode catalyst is characterized in that may further comprise the steps:
1) preparation complex carrier: in reaction vessel, add the sulfuric acid solution that contains dispersant earlier, add multi-walled carbon nano-tubes again, add aniline behind the sonic oscillation, add ammonium persulfate solution again, 0～5 ℃ of reaction back washing down, oven dry, standby, dispersant is selected at least a in Triton X-100 and the polyvinyl alcohol for use, by quality than dispersant: aniline: multi-walled carbon nano-tubes=1～2: 0.67～2: 1;
2) get polyaniline/multi-walled carbon nano-tubes complex carrier powder to reaction vessel, add the acetate buffer solution contain additive, sonic oscillation gets dispersion liquid, and additive is at least a in ethylene glycol, the isopropyl alcohol, the pH=3.5 of acetate buffer solution～4.5;
3) get platinum acid chloride solution and add in the dispersion liquid, continue vibration, by quality than chloroplatinic acid: polyaniline/multi-walled carbon nano-tubes complex carrier powder=0.23～1.4: 1;
4) be warming up to 60～80 ℃, splash into excessive sodium borohydride reduction agent solution reaction back and filter, washing is not dried finished product after having chlorion.
2. DMFC method for preparing anode catalyst as claimed in claim 1 is characterized in that in step 1), and the sonic oscillation time is 2～4h.
3. DMFC method for preparing anode catalyst as claimed in claim 1 is characterized in that in step 1), and 2.4 times of the suitable aniline quality of the addition of ammonium persulfate solution are 6～8h 0～5 ℃ of following reaction time.
4. DMFC method for preparing anode catalyst as claimed in claim 1 is characterized in that in step 1), and the concentration of multi-walled carbon nano-tubes in sulfuric acid solution is 0.5～1mg/ml, and sulfuric acid solution concentration is 1mol/L.
5. DMFC method for preparing anode catalyst as claimed in claim 1 is characterized in that in step 2) in, the sonic oscillation time that adds behind the acetate buffer solution contain additive is 2～4h.
6. DMFC method for preparing anode catalyst as claimed in claim 1, it is characterized in that in step 2) in, polyaniline/the concentration of multi-walled carbon nano-tubes complex carrier powder in acetate buffer solution is 0.5～1mg/ml, and additive capacity is 10%～20% of an acetate buffer solution.
7. DMFC method for preparing anode catalyst as claimed in claim 1 is characterized in that in step 3), and the continuation duration of oscillation is 30～60min.
8. DMFC method for preparing anode catalyst as claimed in claim 1 is characterized in that in step 3), and the concentration of chloroplatinic acid is 0.0386～0.077mmol/L.
9. DMFC method for preparing anode catalyst as claimed in claim 1 is characterized in that in step 4), and the time that splashes into excessive sodium borohydride reduction agent solution reaction is 1～2h, and bake out temperature is 70～80 ℃.
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